JPH0726117B2 - Bleach composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel bleaching composition, and more particularly to an oxygen-based bleaching composition containing a granular coloring composition.

(Prior Art and Its Problems) Conventionally, chlorine-based bleaching agents and oxygen-based bleaching agents are known, but the oxygen-based bleaching agents are widely used in recent years because the former have chlorine odor. Is starting to appear.

These oxygen-based bleaching agents are white granules containing bleaching agents such as sodium percarbonate and sodium perborate as the main components, and are intended to improve the product image of these oxygen-based bleaching agents and to impart a bluing effect to white clothing. Thus, a white bleach granule containing a small amount of a blue-based granular coloring composition added thereto is marketed.

When this blue colored granular additive is not added to the white bleach granules, the bleach granules are simply white odorless powders, sugars commonly used in the home,
There are also situations where it is difficult to distinguish from salt, potato starch, wheat flour, detergent, etc.

In addition, in a household with infants and children, it is easy to mistake the white bleaching agent for food and there is a risk of accidentally putting it in the mouth. In such a case, if a small amount of the colored granules is added, the colored granules can be easily identified and the accident can be prevented.

The present inventors have previously disclosed in JP-B-56-35718 that a granular additive for a bleaching agent comprising a blue pigment and a surfactant having an aromatic sulfonic acid group or an alkali metal base thereof and a bleaching agent containing the same. A composition was proposed. However, when a bleaching composition containing such a small amount of colored granules is used and the cloth is washed and bleached, the blue pigment is dyed on the cloth depending on the method of use, and the cloth after drying has a blue color. There was a considerable risk of spotting. In general, bleached woven fabrics are often white and plain, and there is a drawback that even if a small amount of a blue pigment is dyed on the fabric, contamination is more noticeable. In particular, if you put a small amount of water in a washbasin, soak your clothes, sprinkle a bleach containing colored granules from the top, and leave it as it is without stirring, no matter what pigment you use, Pigment particles deeply penetrated and adhered into the stitch, and spot-like contamination was observed even after sufficient washing with water.

(Means for Solving Problems) As a result of earnest research to solve the above-mentioned drawbacks, the present inventors have found that a granular coloring composition containing a specific dye and an oxygen-based bleaching granule in a solid state. When mixed and stored, the granular coloring composition retains a bright color for a long period of time, but when bleaching clothes and the like, the granular coloring composition dissolves in the bleaching solution, and The dye in the granular coloring composition immediately decomposes and fades due to the oxidizing action of the bleaching agent,
The present invention has been completed by finding that colored stains on a woven fabric can be eliminated.

That is, the present invention is a bleaching composition consisting of a granular coloring composition mainly composed of a water-soluble dye that decomposes and discolors in an oxygen-based bleaching solution, an antioxidant and a water-soluble binder, and an oxygen-based bleaching agent. .

(Function) The most important finding that the present invention has been completed is that a granular coloring composition containing a triphenylmethane dye, a xanthene dye, or another dye having a specific structure among known dyes. The product dissolves uniformly in the oxygen-based bleaching solution and easily decomposes and decolorizes these dyes before adhering to the fibers of clothing and prevents the fabric from being contaminated. In the state where the granular coloring composition is uniformly mixed in a solid state, no decomposition reaction occurs because water does not exist,
This is a technical finding that maintains a stable colored state for a long period of time.

On the other hand, when a conventional pigment is used, when it is added to water, the concentration of the pigment locally increases in the bleaching washing liquid, and the pigment is insoluble and has oxidation resistance as compared with the dye. Therefore, the pigment remains as it is, and the pigment particles may penetrate between the fibers and be physically dyed. On the other hand, in the case of using a specific water-soluble dye in the present invention, the dye is dissolved and diffused in the bleaching agent aqueous solution and further has an oxidative decolorizing property, so that the dye is easily decolorized by the bleaching agent, and the conventional technique is used. The risk of contamination of the bleached woven fabric can be eliminated.

However, when the above granular coloring composition and a solid mixture of an oxygen-based bleaching agent are stored in a closed container, there is no problem in a short period of time, but in the case of long-term storage, the dye decomposes and fades to some extent. However, this causes a problem that the fading of the granular coloring composition gradually progresses. Therefore, in order to impart long-term fading resistance stability of the dye, by adding an antioxidant to the granular coloring composition, it is possible to completely block the influence of nascent oxygen slightly generated in the closed container. , The granular coloring composition keeps its sharpness for a long time,
Does not deteriorate the product image of the bleach composition.

(Preferred Embodiment) Next, the present invention will be described in more detail with reference to preferred embodiments.

As the dye used in the present invention, any dye can be used as long as it is a dye that decomposes and fades in an aqueous solution of an oxygen-based bleaching agent.

The dye that can be preferably used in the present invention is prepared by preparing a 1% by weight aqueous solution of sodium percarbonate and adding 0.1% by weight of the dye therein.
It means that the color of the dye becomes almost imperceptible after about 12 hours by observing the fading state while stirring at 25 ° C with stirring. On the other hand, the dye whose hue can be clearly perceived even after about 12 hours contaminates various woven fabrics which are bleached substances during the bleaching treatment.

For example, preferred dyes include CI Acid Violet 15, 43, 49, CI Acid Blue 1, 7, 9, 15, 22, 83, 90, 93,
100, 103, 104, CI Acid Green 3, 9, 16, CI Basic Violet 1, 3, 14, CI Basic Blue 1, 5, 7, 19, 26, CI Basic Green 1, 4, CI Moldant Violet 1, Triphenylmethane-based water-soluble dyes such as CI Mordant Blue 1, 29, 47, CI Direct Blue 41; CI Acid Red 51, 52, 87, 92, 94, CI Basic Red 1, CI Basic Violet 10, CI Mol Xanthene dyes such as Dant Red 27; CI Acid Blue 74, CI Acid Violet 43, CI Moldant Blue 13 and the like. These dyes can be used alone or in combination of two or more.

The amount of these dyes used is generally in the range of 0.0005% by weight to 5% by weight, preferably 0.001% by weight to 100% by weight, in 100 parts by weight of the granular coloring composition used in the present invention.
The range that occupies 0.5% by weight is good. If the amount of the dye is too large, the color development of the dye is poor and a clear color cannot be obtained.

As the antioxidant to be used in the present invention, any conventionally known one can be used, and preferred examples thereof include L-ascorbic acid and its sodium salt, erythorbic acid and its sodium salt, isopropyl citrate and dibutyl. Hydroxytoluene, DL-α-tocopherol, nordihydrogyaretic acid, butylhydroxyanisole, propyl gallate, 2,2′-methylene-bis (4-methyl-6-tert-butylphenol), dilaurylthiodipropionate , Triphenyl phosphite and the like. These antioxidants can be used alone or in combination of two or more.

The amount of these antioxidants used is the granular coloring composition of the present invention.
The range of 0.01 to 5% by weight in 100 parts by weight is preferable, and the range of 0.05 to 2% by weight is more preferable.

The water-soluble binder used in the present invention not only acts as a protective layer for the dye in an oxidizing atmosphere when added to an oxygen-based bleaching agent, but also a binder and a fluidizing agent when producing a granular coloring composition. And also functions as a dispersant.

As the water-soluble binder used in the present invention, any material may be used as long as it is water-soluble and is a polymer having tackiness when containing water or other relatively high molecular weight material, for example, methyl cellulose. , Carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, sodium alginate, guar gum, gum arabic, gelatin, casein, collagen, chitin,
Water-soluble polymers such as chitosan, polyvinyl alcohol, sodium polyacrylate, polyethylene oxide, polyoxyethyleneoxypropylene copolymer, polyvinylpyrrolidone, etc., propylated naphthalene sulfonate,
Butylated naphthalene sulfonates, naphthalene sulfonate-based surfactants such as formaldehyde condensation products of naphthalene sulfonates, linear alkylbenzene sulfonates having 8 to 22 carbon atoms, α-olefin sulfonates having 8 to 22 carbon atoms, and polyoxy having 8 to 22 carbon atoms. Anionic surfactants such as ethylene alkyl ether sulfates, alkyl phosphate salts having 8 to 22 carbon atoms, polyoxyethylene alkyl ethers having 8 to 22 carbon atoms, polyoxyethylene alkylphenyl ethers having 8 to 22 carbon atoms, carbon Examples thereof include nonionic surfactants such as sorbitan fatty acid esters and glycerin fatty acid esters of the formulas 8 to 22. These water-soluble polymers or surfactants are used alone or in combination, and one kind or a combination of two or more kinds can be used.

The amount of these water-soluble binders is 100
The range of 0.1 to 20% by weight is preferable, and the range of 0.5 to 10% by weight is more preferable.

In the present invention, in addition to the above three components, it is preferable to use various water-soluble salts as base materials, extender pigments, white pigments and the like. These bases have the main purpose of appropriately lowering the dye concentration in the granular coloring composition of the present invention to improve the color developability of the dye and the purpose of better exhibiting the performance of the water-soluble binder. , And other correlates with bleach. For example, preferred examples include sodium tripolyphosphate, sodium carbonate, sodium sulfate, zeolite, talc, titanium oxide and the like. These bases can be used in an amount of preferably about 30 to 98% by weight in 100 parts by weight of the granular coloring composition of the present invention.

The main components of the granular coloring composition used in the present invention are as described above, but chromatic color pigments and other dyes may be used in combination to the extent that contamination of clothing is not recognized. Further, various conventionally known additives can be added to the extent that the objects and effects of the present invention are not impaired. Examples of these additives include enzymes, chelating agents, antifungal agents, and fragrances.

Next, explaining the method for producing the above granular coloring composition, the above components are uniformly mixed, and a liquid, preferably water, is added in an amount such that the mixture has plasticity, and then the usual granulation is performed. A method such as crushing granulation, crushing granulation, extrusion granulation, rotary granulation, or spray granulation, or a fluidized bed granulation method of spraying a water-soluble binder solution on a powder mixture to an appropriate degree. Be grained. The preferred particle size varies depending on the shape and particle size of the bleaching agent as an additive, but usually 8 to
The most common range is about 60 mesh, preferably about 12-28 mesh.

The granular coloring composition obtained as described above is added to various oxygen-based bleaching agents, and any of these oxygen-based bleaching agents may be used so long as it dissolves in water and releases hydrogen peroxide. Those of percarbonate, perborate and pyrophosphate, citrate, sodium sulfate, urea,
One or two hydrogen peroxide adducts such as sodium silicate
Although one or more kinds can be suitably used, sodium percarbonate and sodium perborate are particularly preferable, and any of these bleaching agents can be obtained from the market and used alone or as a mixture in the present invention. Preference is given to granules, for example granules.

The addition ratio of the granular coloring composition varies depending on the dye concentration of the granular coloring composition, the coloring power, etc., but basically it is not less than the level in which the granular coloring composition is easily perceptible in the bleaching agent composition. For example, the granular coloring composition is added in a proportion of 0.5 to 5% by weight. The addition method may be simple mixing.

The bleaching agent composition of the present invention may further contain various components in addition to the above granular coloring composition and oxygen-based bleaching agent.

In this case, the composition of the present invention can be prepared as a bleaching detergent by adding known components such as an inorganic builder, an anionic / nonionic surfactant, an enzyme, a perfume, a fluorescent agent and the like as a bleaching detergent.

Here, examples of the inorganic builder include sodium sulfate, sodium silicate, and sodium tripolyphosphate. The anionic surfactants include sulfonates and sulfates having an alkyl group having about 8 to 22 carbon atoms, alkylbenzene sulfonates having about 9 to 15 alkyl groups, and α-containing about 8 to 22 carbon atoms. Olefin sulfonate,
Examples thereof include fatty acid soaps having about 10 to 22 carbon atoms. Preferred salts are alkali metal salts, particularly preferred sodium salts. As the nonionic surfactant, an ethylene oxide condensate of an alkylphenol having a linear or branched alkyl group having about 6 to 12 carbon atoms, and 5 to 25 mol of ethylene oxide condensed with 1 mol of the alkylphenol, An ethylene oxide condensate of an aliphatic alcohol obtained by condensing 5 to 30 mol of ethylene oxide with 1 mol of an aliphatic alcohol having a straight or branched chain having about 8 to 22 carbon atoms, propylene glycol is condensed with propylene glycol, and Nonionic surfactants such as "Pluronic" trade names obtained by condensing ethylene oxide, mono- or diethanolamides of fatty acids having about 8 to 18 carbon atoms in the acyl moiety, alkyl groups having about 8 to 24 carbon atoms And amine oxides having a methyl group and / or an ethyl group.

Further, as the enzyme that can be incorporated into the bleaching composition of the present invention,
Hydrolase that promotes the addition or removal of water, oxidoreductase that promotes redox, transferase that transfers a group from one molecule to another, alters stains and promotes removal, bond between molecules A ligase or lyase that cleaves and decomposes dirt to promote removal, an enzyme that isomerizes the molecule, chemically alters dirt to promote removal, and the like can be used. Proteases among hydrolases are preferred. Specific examples of proteases include:
Serine protease, pepsin, trypsin, chymotrypsin, collagenase, keratinase, esterase, subtilisin, papain, carboxypeptidases A and B, aminopeptidase and the like can be mentioned. A preferred protease is serine protease. These are, for example, "Alcalase": Novo Industry Co., Ltd. "Esperase": Novo Industry Co., Ltd. "Viroplase": Nagase & Co., Ltd. "Maxatase": Gist Brocades, Inc. "ALP-2": Meiji Seika Co., Ltd. ) "Superase": easily available as a commercial product such as Pfizer. When the enzyme is added, the content of the enzyme in the bleaching composition is 0.01 to 5% by weight
Is preferred.

When the bleaching agent composition of the present invention is prepared as a bleaching detergent, it is preferable to add the peroxide in an amount of 1 to 95% by weight based on the whole bleaching detergent.

(Effect) The bleaching agent composition of the present invention is one in which the above-mentioned specific granular coloring composition is added to a granular or powdery oxygen-based bleaching agent. It is beautiful to the eye because it is mixed, and it does not lose its coloring property even after long-term storage, and has excellent commercial value. Further, it does not cause misuse with other articles having similar appearance, such as sugar, salt, detergent and the like.

Furthermore, in the actual bleaching process, the dye is easily decolorized by the bleaching agent when dissolved in water, so that no spot-like contamination of clothes occurs.

Hereinafter, the present invention will be described more specifically with reference to Reference Examples, Examples, and Comparative Examples. In the text, parts and% are based on weight unless otherwise specified.

Reference Example 1 1.0 part of CI Acid Blue, 40 parts of formaldehyde condensate of sodium naphthalenesulfonate, 10 parts of sodium L-ascorbate, 929 parts of Glauber's salt and 20 parts of titanium oxide were uniformly blended with a high-speed mixer. This with a kneader 60
After stirring and heating up to 0 ° C., 60 parts of water was added and kneaded for 30 minutes, continuously taken out, crushed by a crusher and dried in a fluidized bed. Then, it was sieved to obtain 450 parts of a 12 to 32 mesh blue granular coloring composition.

Reference Example 2 CI acid violet 49 1.0 part, sodium naphthalene sulfonate formaldehyde condensate 40 parts, sodium erythorbate 5 parts, mirabilite 934 parts and titanium oxide 20 parts were compounded according to Reference Example 1 and treated with 12 to 32 mesh. To obtain 500 parts of a purple granular coloring composition.

Reference Example 3 CI Acid Blue 93 1.0 part, isopropyl citrate 5
Part, polyethylene glycol ^# 11,000 40 parts and sodium carbonate 954 parts were compounded according to Reference Example 1 to give 12 to 3
480 parts of a 2-mesh blue granular coloring composition was obtained.

Reference Example 4 CI basic violet 1 1.0 part, DL-α-tocopherol 10 parts, sodium polyacrylate 20% aqueous solution 10
0 parts, 950 parts of Glauber's salt and 19 parts of titanium oxide were blended according to Reference Example 1 to give a 12 to 32 mesh purple granular coloring composition 52.
I got 0 copies.

Reference Example 5 CI Acid Blue 10.5 parts, dibutylhydroxytoluene 5.0 parts, formaldehyde condensate of sodium naphthalene sulfonate 50 parts and sodium carbonate 945 parts were treated according to the prescription of Reference Example 1 to give 12 to 32 mesh blue granular coloring. 480 parts of the composition are obtained.

Reference Example 6 CI Acid Red 52 1.0 part, propyl gallate 5 parts,
Formaldehyde condensate of sodium naphthalene sulfonate
50 parts, 950 parts of Glauber's salt and 10 parts of titanium oxide were blended according to the formulation of Reference Example 1 to obtain 500 parts of a 12 to 32 mesh red granular coloring composition.

Comparative Reference Example 1 450 parts of a 12 to 32 mesh blue granular coloring composition was obtained with exactly the same formulation except for 10 parts of sodium L-ascorbate in Reference Example 1.

Comparative Reference Example 2 400 parts of a 12 to 32 mesh blue granular coloring composition was obtained with exactly the same formulation except for 5 parts of sodium erythorbate in Reference Example 2.

Comparative Reference Example 3 With the exception that only 5 parts of isopropyl citrate was used in Reference Example 3, the same formulation was used to obtain 500 parts of a 12 to 32 mesh blue granular coloring composition.

Comparative Reference Example 4 450 parts of a 12 to 32 mesh blue granular coloring composition was obtained with exactly the same formulation except for 10 parts of DL-α-tocopherol in Reference Example 4.

Examples 1 to 6 and Comparative Examples 1 to 4 5 parts each of the granular coloring compositions obtained in Reference Examples 1 to 6 and Comparative Reference Examples 1 to 4 and 95 parts of sodium percarbonate were lightly blended in a closed container to form a book. Bleaching compositions of the invention and comparative examples were obtained. These were allowed to stand, and after a certain period of time, the fading property of the granular coloring composition therein was visually judged.

The results are shown in Table 1 below, but since those of the present invention contain an antioxidant, almost no fading in the presence of sodium percarbonate is observed, and long-term fading stability is recognized. Was given.

Further, cotton was dipped in 1,000 parts of a 1% aqueous solution of sodium percarbonate, and 0.5 parts of the granular coloring composition obtained in each of Examples 1 to 6 of the present invention and Comparative Examples 1 to 4 was dispersed therein.
After leaving it overnight, it was taken out the next day, and the dyeing property of the dye after washing with water and drying was tested. No dyeing property to cotton was observed at all.

In each of the above examples, similar results were obtained even when sodium perborate was used instead of sodium percarbonate.

Claims (2)

[Claims] 1. A bleaching composition comprising a granular coloring composition mainly composed of a water-soluble dye which decomposes and discolors in an aqueous solution of an oxygen-based bleaching agent, an antioxidant and a water-soluble binder, and an oxygen-based bleaching agent. 2. The bleaching composition according to claim 1, wherein the oxygen-based bleaching agent is a granular material of sodium percarbonate and / or sodium perborate.